Carboamidoalkyl norbornanes, organoleptic uses thereof and process for preparing same

ABSTRACT

Described are compounds having the generic structure: ##STR1## wherein the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond and wherein R 2  is methyl or hydrogen; R 6  is methyl or hydrogen; R 1 , R 3  or R 7  represent methyl or hydrogen, with the proviso that one of R 1 , R 3  and R 7  represents methyl and the other two of R 1 , R 3  and R 7  represent hydrogen; wherein R 4  and R 5  are the same or different and each represents hydrogen or C 1  -C 3  lower alkyl. In addition, organoleptic uses of such compounds are disclosed for augmenting or enhancing the aroma or taste of consumable materials including foodstuffs, chewing gums, toothpastes, medicinal products, chewing tobaccos, smoking tobaccos, smoking tobacco articles, perfumes, perfumed articles (such as liquid or solid anionic, cationic, nonionic or zwitterionic detergents, fabric softeners, dryer-added fabric softener articles, fabric brighteners and other perfumed articles and colognes). Also disclosed is a process for preparing such compounds according to the reaction scheme: ##STR2## wherein R&#34; represents C 1  -C 3  alkyl; m+n=3 with the further proviso that m is 1 or 2 and n is 1 or 2; and wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6  and R 7  are as defined above.

This application is a continuation-in-part of application for U.S.Letters Patent Ser. No. 152,188 filed on July 17, 1980 now abandoned.

BACKGROUND OF THE INVENTION

The present invention relates to carboamidoalkyl norbornanes having thegeneric structure: ##STR3## wherein the dashed line represents acarbon-carbon single bond or a carbon-carbon double bond and wherein R₂is methyl or hydrogen; R₆ is methyl or hydrogen; R₁, R₃ or R₇ representmethyl or hydrogen, with the proviso that one of R₁, R₃ and R₇represents methyl and the other two of R₁, R₃ and R₇ represent hydrogen;wherein R₄ and R₅ are the same or different and each represents hydrogenor C₁ -C₃ lower alkyl, produced by the novel process of our inventionand the novel compositions using one or more of such norbornanederivatives to alter, modify or enhance the aroma of certain consumablematerials including perfumes, perfumed articles, colognes, foodstuffs,chewing gums, toothpastes, medicinal products, chewing tobaccos, smokingtobaccos and smoking tobacco articles.

There has been considerable work performed relating to substances whichcan be used to impart (modify, augment or enhance) fragrances to (or in)various consumable materials. These substances are used to diminish theuse of natural materials some of which may be in short supply and toprovide more uniform properties in the finished product.

Sweet, anise, grapefruit-like and green aroma and taste characteristicsare desirable in several types of foodstuffs, chewing gums, medicinalproducts, toothpastes and chewing tobaccos.

Sweet and fruity aroma and taste nuances are desirable for augmenting orenhancing the aroma and taste of smoking tobaccos, smoking tobaccoarticles and smoking tobacco flavors.

Herbaceous, spearmint, spicy, caraway, basil, powdery, fruity,castoreum-like and anise aroma characteristics are desirable in severaltypes of perfume compositions, perfumed articles and colognes.

Arctander, "Perfume and Flavor Chemicals", 1969, Volume I discloses theuse in perfume compositions and in foodstuff flavors of camphenecarbinyl acetate thus:

"1029: 2,2-Dimethyl-Delta-2-betanorbornane-2-ethylacetate "Camphenecarbinyl acetate". ##STR4## Mild and sweet-woody odor with afloral-piney undertone. The commercial products are probably not welldefined single chemicals, and great variations in odor have beenobserved.

This ester has been developed in line with the research on Sandalwoodtype odors. The parent alcohol "Camphene carbinol" was once considereduseful as a Sandalwood type material, but it has found more use as asweetening and enriching ingredient in sophisticated Pine fragrances.The title ester finds limited use in perfume compositions of woodycharacter, Fougeres, Pine fragrances, etc. and it blends very well withthe Cyclohexanol derivatives, Ionones, iso-Bornylacetate, Nitromusks,etc."

Mellor and Webb, J. Chem. Soc. Perkin Trans II, 1974 (I) 26-31 disclosesproduction of the compounds having the structures: ##STR5## togetherwith several other methyl substituted isomers thereof in admixture,according to the reaction: ##STR6## The Mellor and Webb article,however, does not disclose the reaction to take place at lowtemperatures in the presence of an alkyl aluminum halide or dialkylaluminum halide whereby but two isomers are produced in a controlledfashion in high yields. Furthermore, the Mellor and Webb article doesnot disclose the production of carboamido compounds but is merelylimited to carboalkoxy compounds.

Thus, nothing in the prior art indicates production for organolepticuses of compounds having the generic structure: ##STR7## wherein thedashed line represents a carbon-carbon single bond or a carbon-carbondouble bond and wherein R₂ is methyl or hydrogen; R₆ is methyl orhydrogen; R₁, R₃ or R₇ represent methyl or hydrogen, with the provisothat one of R₁, R₃ and R₇ represents methyl and the other two of R₁, R₃and R₇ represent hydrogen; wherein R₄ and R₅ are the same or differentand each represents hydrogen or C₁ -C₃ lower alkyl.

Belgian Pat. No. 731,124 discloses the butyramide having the structure:##STR8## for use in perfumery. It is indicated that this butyramide hasa minty aroma and taste. The compound having the structure: ##STR9## isdifferent in kind, both insofar as structure is concerned and insofar asorganoleptic properties are concerned from the compounds of the instantinvention.

Belgian Pat. No. 788,461 discloses the use in perfumery ofN-phenyl-N-methyl-2-ethyl butyric acid amide which has the structure:##STR10## It is indicated that this material has an herbaceous scentwith a grapefruit-like note, being useful in perfumes, cosmeticproducts, foodstuffs and drinks. The structure of the compound ofBelgian Pat. No. 788,461 is different in kind from the structure of thecompounds of the instant case, and furthermore, the organolepticproperties of the compound of Belgian Pat. No. 788,461 are different inkind from the organoleptic properties of the compounds of the instantcase.

U.S. Pat. No. 4,193,936 issued on Mar. 18, 1980 (division of Ser. No.796,973, filed on May 16, 1977, now U.S. Pat. No. 4,150,052) disclosessubstantially odorless non-volatile, physiologically active coolingcompositions having the formula: ##STR11## wherein R is C₁ -C₉ alkyl, C₃-C₇ cycloalkyl or a substituted phenyl radical of up to ten carbonatoms, containing as substituents one or more groups selected from C₁-C₄ alkyl, hydroxy, C₁ -C₄ alkoxy, nitro and halogen. The compounds ofU.S. Pat. No. 4,193,936 as well as those of U.S. Pat. No. 4,150,052, aredifferent in kind from the compounds of our invention, and furthermore,their organoleptic properties are different in kind from theorganoleptic properties of the compounds of our invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 represents the GLC profile for the reaction product of Example I,wherein peaks 1, 2, 3 and 4 represent peaks for compounds having thestructures: ##STR12##

FIG. 2 represents the mass spectrum for the reaction product of ExampleI which contains the compounds having the structures: ##STR13##

FIG. 3A represents the NMR spectrum for peak 1 of the GLC profile of thereaction product of Example I which represents the compound having thestructure: ##STR14##

FIG. 3B represents the NMR spectrum for peak 2 of the GLC profile of thereaction product of Example I which represents the compound having thestructure ##STR15##

FIG. 3C represents the NMR spectrum for peak 3 of the GLC profile of thereaction product of Example I and represents the compound having thestructure: ##STR16##

FIG. 3D represents the NMR spectrum for peak 4 of the GLC profile of thereaction product of Example I and represents the compound having thestructure: ##STR17##

FIG. 4A represents the infra-red spectrum for peak 1 of the GLC profileof the reaction product of Example I which represents the compoundhaving the structure: ##STR18##

FIG. 4B represents the infra-red spectrum for peak 2 of the GLC profileof the reaction product of Example I and represents the compound havingthe structure: ##STR19##

FIG. 4C represents the infra-red spectrum for peak 3 of the GLC profileof the reaction product of Example I and represents the compound havingthe structure: ##STR20##

FIG. 4D represents the infra-red spectrum for peak 4 of the GLC profileof the reaction product of Example I and represents the compound havingthe structure: ##STR21##

FIG. 5 represents the mass spectrum for the reaction produced accordingto Example III containing the compounds having the structures: ##STR22##

FIG. 6A represents the infra-red spectrum for fraction 1 of thedistillation product of the reaction product of Example III whichconsists of the compound having the structure: ##STR23##

FIG. 6B represents the NMR spectrum for fraction 1 of the distillationproduct of the reaction product of Example III which consists of thecompound having the structure: ##STR24##

FIG. 7A represents the infra-red spectrum for fraction 8 of thedistillation product of the reaction product of Example II whichconsists of the compound having the structure: ##STR25##

FIG. 7B represents the NMR spectrum for fraction 8 of the distillationproduct of the reaction product of Example II, which consists of thecompound having the structure: ##STR26##

FIG. 8 is the GLC profile for the reaction product of Example XIX(conditions: Carbowax column programmed at 80°-220° C. at 8° C. perminute) containing the compound having the structure: ##STR27##

FIG. 9 is the NMR spectrum for the reaction product of Example XIXcontaining the compound having the structure: ##STR28##

FIG. 10 is the infra-red spectrum for the reaction product of ExampleXIX containing the compound having the structure: ##STR29##

DETAILED DESCRIPTION OF FIG. 1

FIG. 1 represents the GLC profile for the reaction product of Example I.Peak 1 on said FIG. 1 represents the compound having the structure:##STR30## Peak 2 on FIG. 1 also represents the compound having thestructure: ##STR31## Peak 3 on said FIG. 1 represents the compoundhaving the structure: ##STR32## Peak 4 represents the compound havingthe structure: ##STR33## Peak 5 on said FIG. 1 represents the solventpeak on said GLC profile. The ratios of Peak 1: Peak 2: Peak 3: Peak 4:Peak 5 are:

14.76:

14.96:

15.77:

16.22:

3.90

THE INVENTION

It has now been discovered that novel solid and liquid perfumecompositions, colognes and perfumed articles (e.g., solid or liquidanionic, cationic, nonionic or zwitterionic detergents, fabricsofteners, dryer-added fabric softener articles, cosmetic powders andsoaps) having intense and longlasting herbaceous, spearmint, spicy,powdery, floral, basil, caraway, fruity, castoreum-like and anise aromasand novel solid and liquid foodstuff, chewing gum, toothpaste, medicinalproduct, chewing tobacco, smoking tobacco and smoking tobacco articleflavoring compositions, foodstuffs, toothpastes, chewing tobaccos,medicinal products, chewing gum, smoking tobaccos and smoking tobaccoarticles may be provided by the utilization of one or more of thesubstituted norbornane derivatives having the generic structure:##STR34## wherein the dashed line represents a carbon-carbon single bondor a carbon-carbon double bond and wherein R₂ is methyl or hydrogen; R₆is methyl or hydrogen; R₁, R₃ or R₇ represent methyl or hydrogen, withthe proviso that one of R₁, R₃ and R₇ represents methyl and the othertwo of R₁, R₃ and R₇ represent hydrogen; wherein R₄ and R₅ are the sameor different and each represents hydrogen or C₁ -C₃ lower alkyl inperfume compositions, perfumed articles, colognes, foodstuffs, chewinggums, toothpastes, medicinal products, chewing tobaccos, smokingtobaccos and smoking tobacco articles.

Unless otherwise specified, representations herein are intended toindicate "cis" isomers, "trans" isomers, mixtures of "cis" and "trans"isomers and "endo" isomers and "exo" isomers with respect to thenorbornane ring moiety and dextro- and levorotatory isomers, as well asracemic mixtures of obstacle isomers of the norbornane derivatives ofour invention.

Thus, the generic structure: ##STR35## is intended to mean both "endo"and "exo" isomers having the structures: ##STR36##

The novel substituted norbornane derivatives of our invention useful asindicated supra, may be produced by reacting a 1-methylcyclopentadieneor 2-methylcyclopentadiene having one of the structures: ##STR37## or amixture of these methylcyclopentadienes defined according to the genericstructure: ##STR38## with an alkyl acrylamide derivative definedaccording to the generic structure: ##STR39##

Generically, the methylcyclopentadiene derivative structures may beindicated by the generic structure: ##STR40##

The substituted acrylamide structure represents a "cis" isomer or a"trans" isomer, or a mixture of "cis" and "trans" isomers. Thus, the"trans" isomer may be represented by the structure: ##STR41## and the"cis" isomer may be represented by the structure: ##STR42##

The Diels-Alder reaction may be carried out using a specific Lewis acidcatalyst at low temperatures (e.g., 0°-50° C.) or in the absence of acatalyst, at elevated temperature (e.g., 170°-250° C.). Differentisomers and proportions of isomers are produced depending on whether acatalytic reaction is carried out or a non-catalytic thermal Diels-Alderreaction is carried out as will be seen in the examples and subsequentparagraphs, infra.

Thus, when it is desired to carry out a "catalytic" Diels-Alderreaction, the catalyst for this reaction may be an alkyl aluminumdihalide or a dialkyl aluminum halide for example, RAlCl₂ or R₂ AlClwherein R represents methyl, ethyl or n-propyl or i-propyl. Thepreferred catalyst is ethyl aluminum dichloride. Other Lewis acids suchas aluminum trichloride, stannic chloride, zinc chloride, ferricchloride and titanium tetrachloride have been attempted to be used butsuch attempts have proved to be unsuccessful with minimal or no yieldsin the product being produced. The temperature range of the reaction mayvary from about 0° C. up to about 50° C. with ambient temperatures from20° up to 30° C. being preferred. The reaction pressure will not affectthe yield but, conveniently and economically, a reaction pressure ofatmospheric is preferred. Thus, the catalyst for the reaction may bedefined according to the formula:

    R'.sub.n AlCl.sub.m

wherein R' is C₁ -C₃ alkyl and the sum, m+n equals 3, with m being 1 or2 and n being 1 or 2. The resulting reaction mass is a mixture ofcompounds containing unsaturation in the norbornane moiety definedaccording to the generic structure: ##STR43##

These compounds may be used "as is" for their organoleptic properties orthe mixture of compounds may be further hydrogenated using hydrogen gasat supra-atmospheric pressures. When it is desired to use the compounds"as is", for their organoleptic properties, it is preferable to refinethe reaction mass as by fractional distillation thereby creating aproduct usable as set forth above.

When the hydrogenation is carried out on a mixture of compoundscontaining compounds having the structure defined according to thegenus: ##STR44## compounds containing the structures: ##STR45## will beproduced. It is preferable to carry out the hydrogenation at pressuresof from about 20 psig up to about 2000 psig with a pressure range offrom about 40 up to about 80 psig being preferred. It is also preferablefor the reaction to be carried out in the presence of a catalyst such asRainey nickel, Palladium-on-Carbon, Palladium-on-Calcium Carbonate,Palladium-on-Barium Sulfate, and Platinum. When using the Palladium-saltcatalyst, it is preferred to use from about 3% up to about 12%Palladium-on salt, for example, 5% Palladium-on-Calcium Carbonate.

The reaction sequence including the catalytic Diels-Alder reaction whichis embodied within our invention is generically set forth as follows:##STR46## wherein R₂ is methyl or hydrogen; R₆ is methyl or hydrogen;R₁, R₃ or R₇ represent methyl or hydrogen, with the proviso that one ofR₁, R₃ and R₇ represents methyl and the other two of R₁, R₃ and R₇represent hydrogen; wherein R₄ and R₅ are the same or different and eachrepresents hydrogen or C₁ -C₃ lower alkyl.

When it is desired to carry out the thermal non-catalytic Diels-Alderreaction, the reaction takes place at temperatures of between 170° C.and 250° C. at elevated pressures in order to prevent the constituentsof the reaction mass from evaporating. Too low a temperature of reactionwill either give rise to inordinately long times of reaction, yieldswhich are not commercially feasible since they are too low, or noreaction at all. However, temperatures above 250° C. are considered toohigh in that although the reaction is speeded up, the high temperaturegives rise to an uncontrollable reaction and decomposition of reactionproduct which further gives rise to separation problems when attemptingto obtain the substantially pure reaction product usable for itsorganoleptic properties. It has also been found that when carrying outthe thermal reaction in certain instances this reaction is surprisingly,unexpectedly, unobviously and advantageously more specific than the lowtemperature catalytic Diels-Alder reaction. Thus, when reacting themethylcyclopentadiene dimer mixture with dimethylacrylamide according tothe reaction sequence: ##STR47## the reaction product having thestructure: ##STR48## is produced without producing any other isomersthereof. This reaction product is the "endo" isomer of a specificisomeric product that would be expected to be one of many reactionproducts but that is, in fact, the only isomer produced.

Notwithstanding the foregoing statement, however, both the catalyticDiels-Alder reaction and the non-catalytic thermal Diels-Alder reaction,as a general rule, give rise to mixtures of isomers albeit differentmixtures of isomers in different proportions.

When the norbornane derivative(s) of our invention are used as foodflavor adjuvants or medicinal product flavor adjuvants or toothpasteflavor adjuvants or chewing gum flavor adjuvants, the nature of theco-ingredients included with each of said norbornane derivative(s) informulating the product composition will also serve to augment orenhance the organoleptic characteristics of the ultimate foodstuff,chewing gum, medicinal product, toothpaste or chewing tobacco treatedtherewith.

Substances suitable for use herein as co-ingredients or flavoringadjuvants are well known in the art for such use, being extensivelydescribed in the relevant literature. It is required that any suchmaterial be "ingestibly acceptable", and thus non-toxic or otherwisenon-deleterious, particularly from an organoleptic standpoint wherebythe ultimate flavor and/or aroma of the consumable material used doesnot cause the consumable material to have unacceptable aroma or tastenuances.

It is a further requirement that such material be organolepticallycompatible with the foodstuff with which it is used so that the flavorand aroma nuances of such material taken together with the flavor andaroma nuances of the foodstuff (as a whole) give rise to a harmoniouslyaesthetically pleasing aroma and taste profile. Such materials, ingeneral, may be characterized as flavoring adjuvants or vehiclescomprising broadly, stabilizers, thickeners, surface active agents,conditioners, other flavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride,antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid,butylated hydroxy-anisole (mixture of 2- and3-tertiary-butyl-4-hydroxy-anisole), butylated hydroxy toluene(2,6-di-tertiary-butyl-4-methyl phenol), propyl gallate and the like andsequestrants, e.g. citric acid.

Thickener compounds include carriers, binders, protective colloids,suspending agents, emulsifiers and the like, e.g., agar agar,carrageenan, cellulose and cellulose derivatives such as carboxymethylcellulose and methyl cellulose; natural and synthetic gums such as gumarabic, gum tragacanth; gelatin, proteinaceous materials, lipids;carbohydrates; starches, pectins, and emulsifiers, e.g., mono- anddiglycerides of fatty acids, skim milk powder, hexoses, pentoses,disaccharides, e.g., sucrose corn syrup and the like.

Surface active agents include emulsifying agents, e.g., fatty acids suchas, palmitic acid, myristic acid and the like, mono- and diglycerides offatty acids, lecithin, defoaming and flavor-dispersing agents such assorbitan monostearate, potassium monostearate, hydrogenated tallowalcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and thelike; starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like, buffersand neutralizing agents, e.g., sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar and the like;colorants, e.g., carminic acid, cochineal, tumeric, cur-cumin and thelike; firming agents such as aluminum sodium sulfate, calcium chlorideand calcium gluconate; texturizers, anti-caking agents, e.g., aluminumcalcium sulfate and tribasic calcium phosphate; enzymes; yeast foods,e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g.,iron salts such as ferric phosphate, ferrous gluconate and the like,riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfateand the like.

Other flavorants and flavor intensifiers include organic acids, e.g.,acetic acid, formic acid, 2-hexenoic acid, benzoic acid, n-butyric acid,caproic acid, caprylic acid, cinnamic acid, isobutyric acid, isovalericacid, alpha-methylbutyric acid, propionic acid, valeric acid,2-methyl-2-pentenoic acid, 2-methyl-cis-3-pentenoic acid; ketones andaldehydes, e.g. octanal, n-decanal, acetaldehyde, acetophenone, acetone,acetyl methyl carbinol, acrolein, n-butanol, crotonal, diacetyl,2-methyl butanal, beta, beta-dimethyl-acrolein, methyl-n-amyl ketone,n-hexenal, 2-hexenal, isopentanal, hydrocinnamic aldehyde,cis-3-hexenal, 2-heptenal, nonyl aldehyde, citral,4-(p-hydroxyphenyl)-2-butanone, alphaionone, beta-ionone,2-methyl-3-butanone, benzaldehyde, damascone, damascenone, acetophenone,2-heptanone, o-hydroxyacetophenone, 2-methyl-2-hepten-6-one, 2-octanone,2-undecanone, 3-phenyl-4-pentenal, 2-phenyl-2-hexenal,2-phenyl-2-pentenal, furfural, 5-methyl furfural, cinnamaldehyde,β-cyclohomocitral, 2-pentanone, 2-pentenal and propanal; alcohols suchas 1-butanol, benzyl alcohol, 1-borneol, trans-2-buten-1-ol, ethanol,geraniol, 1-hexanol, 2-heptanol, trans-2-hexenol-1, cis-3-hexen1-ol,3-methyl-3-buten-1-ol, 1-pentanol, 1-penten-3-ol,p-hydroxyphenyl-2-ethanol, isoamyl alcohol, fenchyl alcohol, isofenchylalcohol, phenyl-2-ethanol, α-terpineol, cis-terpineol hydrate, eugenol,linalool, 2-heptanol, acetoin; esters such as butyl acetate, ethylacetate, ethyl acetoacetate, ethyl benzoate, ethyl butyrate, ethylcaprate, ethyl caproate, ethyl caprylate, ethyl cinnamate, ethylcrotonate, ethyl formate, ethyl isobutyrate, ethyl isovalerate, ethyllaurate, ethyl myristate, ethyl α-methyl-butyrate, ethyl propionate,ethyl salicylate, trans-2-hexenyl acetate, hexyl acetate, 2-hexenylbutyrate, hexyl butyrate, isoamyl acetate, isopropyl butyrate,dimethylanthranilate, methyl acetate, methyl butyrate, methyl caproate,methyl isobutyrate, α-methylphenylglycidate, ethyl succinate, isobutylcinnamate, cinnamyl formate, methyl cinnamate, and terpinyl acetate;hydrocarbons such as dimethyl naphthalene, dodecane, methyl diphenyl,methyl naphthalene, myrcene, cadinene, limonene, nephthalene,octadecane, tetradecane, tetramethyl naphthalene, tridecane, trimethylnaphthalene, undecane, caryophyllene, 1-phellandrene, p-cymene,1-α-pinene; pyrazines such as 2,3-dimethylpyrazine,2,5-dimethylpyrazine, 2,6-dimethylpyrazine, 3-ethyl-2,5dimethylpyrazine,2-ethyl-3,5,6-trimethylpyrazine, 3-isoamyl-2, 5-dimethyl-pyrazine,5-isoamyl-2,3-dimethylpyrazine, 2-isoamyl3,5,6-trimethylpyrazine,isopropyl dimethylpyrazine, α-methyl-3-ethylpyrazine,tetramethylpyrazine, trimethylpyrazine; essential oils, such as jasmineabsolute, cassia oil, cinnamon bark oil, rose absolute, orris absolute,lemon essential oil, orange essential oil, grapefruit oil, Bulgarialrose, yara yara and vanilla; lactones such as gammanonalactone;sulfides, e.g., methyl sulfide and other materials such as maltol andacetals (e.g., 1,1-diethoxyethane, 1,1-dimethoxyethane anddimethoxyethane).

The specific flavoring adjuvants selected for use may be either solid orliquid depending upon the desired physical form of the ultimate product,i.e., foodstuff, whether simulated or natural, and should, in any event,(i) be organoleptically compatible with the norbornane derivative(s) ofour invention by not covering or spoiling the organoleptic properties(aroma and/or taste) thereof; (ii) be non-reactive with the norbornanederivative(s) of our invention; and (iii) be capable of providing anenvironment in which the norbornane derivative(s) can be dispersed oradmixed to provide a homogeneous medium. In addition, selection of oneor more flavoring adjuvants, as well as the quantities thereof willdepend upon the precise organoleptic character desired in the finishedproduct. Thus, in the case of flavoring compositions, ingredientselection will vary in accordance with the foodstuff, chewing gum,medicinal product or toothpaste to which the flavor and/or aroma are tobe imparted, modified, augmented or enhanced. In contradistinction, inthe preparation of solid products, e.g., simulated food-stuffs,ingredients capable of providing normally solid compositions should beselected such as various cellulose derivatives.

As will be appreciated by those skilled in the art, the amount ofnorbornane derivative(s) employed in a particular instance can vary overa relatively wide range, depending upon the desired organoleptic effectsto be achieved. Thus, correspondingly, greater amounts would benecessary in those instances wherein the ultimate food composition to beflavored is relatively bland to the taste, whereas relatively minorquantities may suffice for purposes of enhancing the composition merelydeficient in natural flavor and aroma. The primary requirement is thatthe amount selected be effective i.e., sufficient to augment or enhancethe organoleptic characteristics of the parent composition, whetherfoodstuff per se, chewing gum per se, medicinal product per se,toothpaste per se, chewing tobacco per se, or flavoring composition.

The use of insufficient quantities of norbornane derivative(s) will, ofcourse, substantially vitiate any possibility of obtaining the desiredresults while excess quantities prove needlessly costly and, in extremecases, may disrupt the flavor-aroma balance, thus provingself-defeating. Accordingly, the terminology "effective amount" and"sufficient amount" is to be accorded a significance in the context ofthe present invention consistent with the obtention of desired flavoringeffects.

Thus, and with respect to ultimate food compositions, chewing gumcompositions, medicinal product compositions, toothpaste compositionsand chewing tobaccos compositions, it is found that quantities ofnorbornane derivative(s) ranging from a small but effective amount,e.g., 0.002 parts per million (ppm) up to about 50 parts per million(ppm) based on total composition are suitable. Concentrations in excessof the maximum quantity stated are not normally recommended, since theyfail to provide commensurate enhancement of organoleptic properties. Inthose instances, where the norbornane derivative(s) is added to thefoodstuff as an integral component of a flavoring composition, it is, ofcourse, essential that the total quantity of flavoring compositionemployed be sufficient to yield an effective norbornane derivative (s)concentration in the foodstuff product.

Food flavoring compositions prepared in accordance with the presentinvention preferably contain the norbornane derivative(s) inconcentrations ranging from about 0.005% up to about 5% by weight basedon the total weight of the said flavoring composition.

The composition described herein can be prepared according toconventional techniques well known as typified by cake batters and fruitdrinks and can be formulated by merely admixing the involved ingredientswithin the proportions stated in a suitable blender to obtain thedesired consistency, homogeneity of dispersion, etc. Alternatively,flavoring compositions in the form of particulate solids can beconveniently prepared by mixing the norbornane derivative(s) of ourinvention with, for example, gum arabic, gum tragacanth, carrageenan andthe like, and thereafter spray-drying the resultant mixture whereby toobtain the particulate solid product. Pre-prepared flavor mixes inpowder form, e.g., fruit-flavored powder mixes are obtained by mixingthe dried solid components, e.g., starch, sugar and the like and thenorbornane derivative(s) in a dry blender until the requisite degree ofuniformity is achieved.

It is presently preferred to combine with the norbornane derivative(s)of our invention, the following adjuvants:

Bergamot oil;

Citral;

Amyl alcohol;

Ethyl acetate;

5 phenyl-4-pentenal;

5 phenyl-2-pentenal;

n-Octanal;

n-Decanal;

Limonene;

Geraniol;

Cadinene;

Dimethylanthranilate;

Vanillin;

Amyl butyrate;

2-(n-pentyl)-thiazole;

2-(i-butyl)-thiazole;

2-(i-propyl)-thiazole;

2-(n-propyl)-thiazole;

The dimethyl acetal of 2-phenyl-4-pentenal;

Methional;

4-Methylthiobutanal;

2-Ethyl-3-acetyl pyrazine;

Tetramethyl pyrazine;

2-Methyl pyrazine;

2-Trans hexenal;

Maltol;

2-Phenyl-4-penetenal;

2-Phenyl-4-penetenal dimethyl acetal; and

2-Phenyl-4-penetenal diethyl acetal.

The norbornane derivative(s) and one or more auxiliary perfumeingredients, including, for example, hydrocarbons, alcohols, ketones,aldehydes, nitriles, esters, lactones or cyclic esters, syntheticessential oils and natural essential oils, may be admixed so that thecombined odors of the individual components produce a pleasant anddesired fragrance, particularly and preferably in herbaceous, spearmint,spicy, powdery, floral, basil, caraway, fruity, castoreum-like and anisefragrances. Such perfume compositions usually contain (a) the main noteor the "bouquet" or foundation stone of the composition; (b) modifierswhich round off and accompany the main note; (c) fixatives which includeodorous substances which lend a particular note to the perfumethroughout all stages of evaporation and substances which retardevaporation; and (d) topnotes which are usually low boiling,fresh-smelling materials.

In perfume compositions, it is the individual components whichcontribute to their particular olfactory characteristics, however, theoverall sensory effect of the perfume composition will be at least thesum total of the effects of each of the ingredients. Thus, one or moreof the norbornane derivative(s) of our invention can be used to alter,modify or enhance the aroma characteristics of a perfume composition,for example, by utilizing or moderating the olfactory reactioncontributed by another ingredient in the composition.

The amount of norbornane derivative(s) of our invention which will beeffective in perfume compositions as well as perfumed articles andcolognes depends on many factors, including the other ingredients, theiramounts and the effects which are desired. It has been found thatperfume compositions containing as little as 0.01% of norbornanederivative(s) or even less (e.g., 0.005%) can be used to impart aherbaceous, spearmint, spicy, powdery, floral, basil, caraway, fruity,castoreum-like and anise aroma to soaps, detergents (including anionic,nonionic, cationic and zwitterionic solid or liquid detergents),cosmetics, fabric softeners, dryer-added fabric softener articles,fabric whiteners, optical brightener compositions, hair preparations andother products. The amount employed can range up to 70% of the fragrancecomponents and will depend on considerations of cost, nature of the endproduct, the effect desired on the finished product and the particularfragrance sought.

The norbornane derivative(s) of our invention are useful (taken alone ortogether with other ingredients in perfume compositions) in detergentsand soaps, space odorants and deodorants, perfumes, colognes, toiletwater, bath preparations such as lacquers, brilliantines, pomades andshampoos; cosmetic preparations, such as creams, deodorants, handlotions and sun screens; powders such as talcs, dusting powders, facepowders and the like. As little as 0.005% of the norbornanederivative(s) (in the ultimate perfumed article) will suffice to impartan intense herbaceous, spearmint, spicy, powdery, floral, basil,caraway, fruity, castoreum-like and anise fragrance to various types ofperfumed articles. Generally no more than 3% of the norbornanederivatives based on the ultimate end product (perfumed article) isrequired.

In addition, the perfume composition or fragrance composition of ourinvention can contain a vehicle, or carrier for the norbornanederivative(s). The vehicle can be a liquid such as a non-toxic alcohol,a non-toxic glycol, or the like. The carrier can also be an absorbentsolid, such as a gum (e.g., gum arabic), or components for encapsulatingthe composition (such as gelatin).

An addition aspect of our invention provides an organolepticallyimproved smoking tobacco product and additives therefor, as well asmethods of making the same which overcome problems heretoforeencountered in which desired sweet, fruity flavor characteristics andaroma characteristics of natural tobacco (prior to smoking and onsmoking in the main stream and in the side stream) are created orenhanced or modified or augmented and may be readily controlled andmaintained at the desired uniform level regardless of variations in thetobacco components of the blend.

This invention further provides improved tobacco additives and methodswhereby various natural aromatic tobacco flavoring characteristics withsweet and fruity notes may be imparted to smoking tobacco products andmay be readily varied and controlled to produce the desired uniformflavoring characteristics.

In carrying out this aspect of our invention, we add to smoking tobaccomaterials or a suitable substitute therefor (e.g., dried lettuce leaves)an aroma and flavor additive containing as an active ingredient one ormore norbornane derivatives of our invention.

In addition to the norbornane derivatives of our invention, otherflavoring and aroma additives may be added to the smoking tobaccomaterial or substitute therefor either separately or in mixture with thenorbornane derivatives as follows:

I. Synthetic Materials

Beta-ethyl-cinnamaldehyde;

Eugenol;

Dipentene;

Damascenone;

Maltol;

Ethyl maltol;

Delta undecalactone;

Delta decalactone;

Benzaldehyde;

Amyl acetate;

Ethyl butyrate;

Ethyl valerate;

Ethyl acetate;

2-Hexenol-1;

2-Methyl-5-isopropyl-1,3-nonadiene-8-one;

2,6-Dimethyl-2,6-undecadiene-10-one;

2-Methyl-5-isopropylacetophenone;

2-Hydroxy-2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)-decahydronaphthalene;

Dodecahydro-3a,6,6,9a-tetramethylnaphtho-(2,1-b-)-furan

4-Hydroxyhexanoic acid, gamma lactone; and

Polyisoprenoid hydrocarbons defined in Example V of U.S. Pat. No.3,589,372, issued on June 29, 1971.

II. Natural Oils

Celery seed oil;

Coffee extract;

Bergamot oil;

Cocoa extract;

Nutmeg oil; and

Origanum oil.

An aroma and flavoring concentrate containing one or more norbornanederivatives of our invention and, if desired, one or more of the aboveindicated additional flavoring additives may be added to the smokingtobacco material, to the filter or to the leaf or paper wrapper. Thesmoking tobacco material may be shredded, cured, cased and blendedtobacco material or reconstituted tobacco material or tobaccosubstitutes (e.g. lettuce leaves) or mixtures thereof. The proportionsof flavoring additives may be varied in accordance with taste butinsofar as enhancement or the imparting of sweet and/or fruity notes, wehave found that satisfactory results are obtained if the proportion byweight of the sum total of norbornane derivative(s) to smoking tobaccomaterial is between 50 ppm and 1,500 ppm (0.015%-0.15%). We have furtherfound that satisfactory results are obtained if the proportions byweight of the sum total of norbornane derivative used to flavoringmaterial is between 1,500 and 15,000 ppm (0.15%-1.5%).

Any convenient method for incorporating the norbornane derivative(s)into the tobacco product may be employed. Thus, the norbornanederivative(s) taken alone or along with other flavoring additives may bedissolved in a suitable solvent such as ethanol, diethyl ether and/orvolative organic solvents and the resulting solution may either bespread on the cured, cased and blended tobacco material or the tobaccomaterial may be dipped into such solution. Under certain circumstances,a solution of the norbornane derivative(s) taken alone or taken furthertogether with other flavoring additives as set forth above, may beapplied by means of a suitable applicator such as a brush or roller onthe paper or leaf wrapper for the smoking product, or it may be appliedto the filter by either spraying or dipping or coating.

Furthermore, it will be apparent that only a portion of the tobacco orsubstitute therefor need be treated and the thus treated tobacco may beblended with other tobaccos before the ultimate tobacco product isformed. In such cases, the tobacco treated by the norbornanederivative(s) have in excess of the amounts or concentrations aboveindicated so that when blended with other tobaccos, the final productwill have the percentage within the indicated range.

In accordance with one specific example of our invention an aged, curedand shredded domestic burley tobacco is sprayed with a 20% ethanolsolution of the compound having the structure: ##STR49## in an amount ofmixture to provide tobacco composition containing 800 ppm by weight ofthe mixture of the amide on a dry basis. Thereafter the alcohol isremoved by evaporation and the tobacco is manufactured into cigarettesby the usual techniques. The cigarette when treated as indicated has adesired and pleasing aroma which is detectable in the main stream andthe side stream when the cigarette is smoked. This aroma is described asbeing sweeter, fruity, more aromatic, more tobacco-like having sweet,fruity notes.

While our invention is particularly useful in the manufacture of smokingtobacco such as cigarette tobacco, cigar tobacco and pipe tobacco, othertobacco products formed from sheeted tobacco dust or fines may also beused. Likewise, the norbornane derivative(s) of our invention can beincorporated with materials such as filter tip materials (e.g.,cellulose acetate filters wherein sweet, fruity effects are desired),seam paste, packaging materials and the like which are used along withtobacco to form a product adapted for smoking. Furthermore, thenorbornane derivative(s) can be added to certain tobacco substitutes ofnatural or synthetic origin (e.g., dried lettuce leaves) and,accordingly, by the term "tobacco" as used throughout this specificationis meant any composition intended for human consumption by smoking orotherwise, whether composed of tobacco plant parts or substitutematerials or both.

It will thus be apparent that the norbornane derivative(s) of ourinvention can be utilized to alter, modify or enhance sensoryproperties, particularly organoleptic properties such as fragrances of avariety of consumable materials including perfume compositions, perfumedarticles and colognes and such as aromas and tastes of a variety ofconsumable materials including smoking tobacco compositions, smokingtobacco articles, food-stuffs, chewing gums, toothpastes, chewingtobaccos and medicinal products.

The following examples serve to illustrate processes for specificallyproducing the norbornane derivative(s) useful in our invention.

The following examples also serve to illustrate specific embodiments ofour invention.

It will be understood that these examples are illustrative and theinvention is to be considered to be restricted thereto only as indicatedin the appended claims.

All parts and percentages given herein are by weight unless otherwisespecified.

EXAMPLE I PREPARATION OF 1- AND 5-METHYL-5-NORBORNENE-2-CARBOXYLIC ACIDAMIDES (CATALYTIC DIELS-ALDER REACTION)

Reaction: ##STR50##

Into a 1 liter reaction flask, equipped with thermometer, stirrer,condenser, addition funnel, cooling bath and nitrogen purge are placed200 grams of M, N-dimethyl acrylamide and 300 ml. toluene. Whilemaintaining the reaction at temperature at 20°-25° C., over a period oftwenty minutes, 50 grams of 25% ethyl aluminum dichloride is addeddropwise to the reaction mass. After the addition of the ethyl aluminumdichloride is complete, over a period of twenty-five minutes whilemaintaining the reaction temperature at 20°-25° C., 325 grams of a 50%solution of methyl cyclopentadiene in toluene is added to the reactionmass dropwise. After the addition of the methyl cyclopentadienesolution, the reaction mass is then quenched by pouring same into 500ml. of a 10% sodium chloride solution. The aqueous phase and the organicphase are separated, and the aqueous phase is extracted with one 200 mlportion of toluene. The organic phases are combined and washed with two500 ml portions of 10% sodium chloride solution. The solvent is thenstripped off of the organic phase and the reaction mass is distilledyielding the following fractions:

    ______________________________________                                               Vapor    Liquid                 Weight of                              Fraction                                                                             Temp.    Temp.    mm/Hg. Reflux Fraction                               No.    (°C.)                                                                           (°C.)                                                                           Pressure                                                                             Ratio  (g.)                                   ______________________________________                                        1      48/35    110/110  2.0    9:1    12                                     2      75       123      1.0    9:1    20.3                                   3      78       129      1.0    9:1    24.3                                   4      79       129      1.0    9:1    22                                     5      84       129      1.0    9:1    29.3                                   6      84       129      1.0    9:1    29.5                                   7      85       130      1.0    9:1    27.5                                   8      85       131      1.0    9:1    27.5                                   9      85       132      1.0    9:1    26                                     10     85       134      1.0    9:1    29.4                                   11     87       179      1.0    9:1    13.5                                   12     83       240      1.0    9:1    4.5                                    ______________________________________                                    

after adding to the reaction mixture 9 grams of Primol®, 0.5 grams ofIonox® and 5 grams of calcium carbonate.

The resulting reaction product contains compounds having the structures:##STR51## as confirmed by NMR mass spectral and IR analyses.

FIG. 1 represents the GLC profile for the reaction product of Example I,wherein peaks 1,2,3 and 4 represent peaks for compounds having thestructures: ##STR52##

FIG. 2 represents the mass spectrum for the reaction product for thereaction product of Example I which contains the compounds having thestructures: ##STR53##

FIG. 3A represents the NMR spectrum for peak 1 of the GLC profile of thereaction product of Example I which represents the compound having thestructure: ##STR54##

FIG. 3B represents the NMR spectrum for peak 2 of the GLC profile of thereaction product of Example I which represents the compound having thestructure ##STR55##

FIG. 3C represents the NMR spectrum for peak 3 of the GLC profile of thereaction product of Example I and represents the compound having thestructure: ##STR56##

FIG. 3D represents the NMR spectrum for peak 4 of the GlC profile of thereaction product of Example I and represents the compound having thestructure: ##STR57##

FIG. 4A represents the infra-red spectrum for peak 1 of the GLC profileof the reaction product of Example I which represents the compoundhaving the structure: ##STR58##

FIG. 4B represents the infra-red spectrum for peak 2 of the GLC profileof the reaction product of Example I and represents the compound havingthe structure: ##STR59##

FIG. 4C represents the infra-red spectrum for peak 3 of the GLC profileof the reaction product of Example I and represents the compound havingthe structure: ##STR60##

FIG. 4D represents the infra-red spectrum for peak 4 of the GLC profileof the reaction product of Example I and represents the compound havingthe structure: ##STR61##

EXAMPLE II

The following minty, floral and herbal type formula are prepared:

    ______________________________________                                        Ingredient         Parts by Weight                                            ______________________________________                                        Geranium Bourbon   20.0                                                       Rosemary Oil Spanish                                                                             10.0                                                       Lavender Oil Barreme                                                                             10.0                                                       Thyme Oil White    10.0                                                       Amyl Cinnamic Aldehyde                                                                           10.0                                                       Sauge Sclaree French                                                                             5.0                                                        Sandalwood Oil     5.0                                                        Galbanum Oil       5.0                                                        Patchouli Oil Light                                                                              5.0                                                        Cedarwood Oil Light                                                                              15.0                                                       Product produced according                                                                       45.0                                                       to Example I, bulked frac-                                                    tions 1-8 containing and                                                      consisting of the compounds                                                   having the structures:                                                         ##STR62##                                                                    and                                                                            ##STR63##                                                                    ______________________________________                                    

When the composition of matter prepared according to Example I isincorporated into the formula at 45.0%, the composition of matter hasadded to it a pleasant, herbaceous, spearmint, spicy, powdery, floral,basis, caraway and anise aroma to the already spicy, herbal and floraltype formulation.

EXAMPLE III PREPARATION OF 1- and 5-METHYL-5-NORBORNANE-2-CARBOXYLICACID AMIDES

Reaction: ##STR64##

Into a 500 ml. pressure bottle equipped with Parr shaker is placed 200grams of the reaction product of Example I containing the compoundshaving the structures: ##STR65## 4 grams of Rainey nickel and 50 ml. ofisopropyl alcohol. The reaction mixture is pressurized to 50 psig afterthe pressure bottle is closed and the reaction mass is purged five timeswith hydrogen in order to remove any air. Over a period of nine hours,while maintaining the reaction pressure at 25-50 psig, hydrogen gas isadded to the reaction mass (total up-take 91 psig hydrogen).

At the end of the reaction, the pressure bottle is opened and thecatalyst is filtered and the solvent is stripped off. The reactionproduct is then distilled on a 12 inch Silver Mirror Goodloe columnyielding the following fractions:

    ______________________________________                                               Vapor    Liquid                 Weight of                              Fraction                                                                             Temp.    Temp.    mm/Hg  Reflux Fraction                               No.    (°C.)                                                                           (°C.)                                                                           Pressure                                                                             Ratio  (g.)                                   ______________________________________                                        1      63/66    111/111  0.8/0.8                                                                              9:1    19.7                                   2      65       111      0.6    9:1    21.5                                   3      80       111      1.0    9:1    24.8                                   4      85       111      1.0    9:1    22.1                                   5      85       111      1.0    9:1    20.1                                   6      85       111      1.0    9:1    26.6                                   7      85       119      1.0    9:1    29.4                                   8      84       210      1.0    9:1    8.8                                    ______________________________________                                    

NMR, IR and mass spectral analysis yield the information that theresulting product contains the compounds having the structures:##STR66##

The distillation as set forth above is carried out with 6 grams ofPrimol® and 0.5 grams of Ionox®.

FIG. 5 is the mass spectrum for the reaction product produced accordingto this example containing the compounds having the structures:##STR67## Bulked fractions 3-8 have a peppery, herbaceous, spearmint,caraway aroma with basil and aniseed undertones.

FIG. 6A represents the infra-red spectrum for fraction 1 of thedistillation product of the reaction product of Example III whichconsists of the compound having the structure: ##STR68##

FIG. 6B represents the NMR spectrum for fraction 1 of the distillationproduct of the reaction product of Example III which consists of thecompound having the structure: ##STR69##

FIG. 7A represents the infra-red spectrum for fraction 8 of thedistillation of the reaction product of Example II, which consists ofthe compound having the structure: ##STR70##

FIG. 7B represents the NMR spectrum for fraction 8 of the distillationproduct of the reaction product of Example II, which consists of thecompound having the structure: ##STR71##

EXAMPLE IV

The following minty, floral and herbal type formula are prepared:

    ______________________________________                                        Ingredient         Parts by Weight                                            ______________________________________                                        Geranium Bourbon   20.0                                                       Rosemary Oil Spanish                                                                             10.0                                                       Lavender Oil Barreme                                                                             10.0                                                       Thyme Oil White    10.0                                                       Amyl Cinnamic Aldehyde                                                                           10.0                                                       Sauge Sclaree French                                                                             5.0                                                        Sandalwood Oil     5.0                                                        Galbanum Oil       5.0                                                        Patchouli Oil Light                                                                              5.0                                                        Cedarwood Oil Light                                                                              15.0                                                       Product produced according                                                    to Example III, bulked                                                        fractions 3-8 containing                                                      and consisting of the                                                         compounds having the                                                          structures:                                                                    ##STR72##                                                                    and                                                                            ##STR73##                                                                    ______________________________________                                    

When the composition of matter prepared according to Example III isincorporated into the formula at 45.0%, the composition of matter hasadded to it a pleasant, peppery, herbaceous, spearmint, caraway aromawith basil and aniseed undertones to this already spicy, herbal andfloral type formulation.

EXAMPLE V

A stable lotion is prepared with the following formulations:

    ______________________________________                                        Ingredients           Parts by Weight                                         ______________________________________                                        Poly(N,N-dimethyl-3,5-dimethyl-                                                                     1.0                                                     ene piperidinium chloride)                                                    (Merquat 100, Merck & Co., U.S.A.,                                            average molecular weight 50,000-                                              100,000, viscosity in 40% aqueous                                             solution, 10,000 cps.                                                         Cocoamidopropyl dimethyl glycine                                                                    5.7                                                     (betaine)                                                                     Myristyl dimethylamine oxide                                                                        12.0                                                    Stearic monoethanolamide opacifier                                                                  2.0                                                     Perfume material as indicated in                                                                    0.5                                                     Table I (below) giving rise to                                                the aroma profiles as indicated                                               in Table I (below)                                                            Water, colour, salts, U.V.                                                    absorber              q.s. to 100                                             ______________________________________                                    

Two or three bottle capfuls of the above lotion held under the tapreleasing the water into the bathtub yields a copiously foamed bubblebath with no visible precipitation flocculation, or "bathtub ring" evenusing hard water. Bathing in this bath is found to have a cleansing andpleasing emollient effect on the skin as described above.

When, after immersion in this bath, the body is soaped, rinsed anddried, an even better, more lasting emollient moisturizing effect on theskin is observed. The foam or bubbles are substantially unaffected bythe soaping step, and no precipitate, flocculate or "bathtub ring", orany bothersome film or coating on the bathtub surface is found.

The aroma produced is as set forth in Table I below:

                  TABLE I                                                         ______________________________________                                        Product             Aroma Profile                                             ______________________________________                                        Product produced according to                                                                     Herbaceous, spearmint,                                    Example I, bulked fractions                                                                       spicy, powdery and                                        1-8 consisting of compounds                                                                       anise aroma                                               having the structures:                                                         ##STR74##                                                                    and                                                                            ##STR75##                                                                    Perfume composition prepared                                                                      A minty, spicy, herbal                                    according to Example II                                                                           and floral aroma                                                              increasing in intensity                                                       on dry-out                                                Product produced according to                                                                     Peppery, herbaceous,                                      Example III, bulked fractions                                                                     spearmint, caraway                                        3-8, consisting of the compounds                                                                  aroma with basil and                                      having the structures:                                                                            aniseed undertones                                         ##STR76##                                                                    and                                                                            ##STR77##                                                                    Perfume compositions prepared                                                                     A minty, spicy, herbal                                    according to Example IV                                                                           and floral aroma                                                              increasing in intensity                                                       on dry-out                                                ______________________________________                                    

EXAMPLE VI

The following formulation is prepared with results and properties anduse similar to those described in Example III.

    ______________________________________                                        Ingredients          Parts by Weight                                          ______________________________________                                        "Merquat 100"        1.0                                                      Cocoamidopropyl dimethyl glycine                                                                   8.0                                                      Myristyl dimethyl amine oxide                                                                      16.0                                                     Perfume ingredient as set forth                                                                    0.8                                                      in Table II (below) giving rise                                               to the aroma profiles as set                                                  forth in Table II (below)                                                     Water                q.s. to 100                                              ______________________________________                                    

The composition is a clear liquid. Its viscosity may be increased byaddition of a lauric or myristic diethanolamide or a solublepolyethylene glycol ester such as polyethylene glycol 6000. In addition,this composition may be rendered opaque by addition of stearicmonoethanolamide stearate, polyethylene glycol 600 monostearate or aglyco amido stearate such as "Cerasynt 1P".

                  TABLE II                                                        ______________________________________                                        Product             Aroma Profile                                             ______________________________________                                        Product produced according                                                                        Herbaceous, spearmint,                                    Example I, bulked fractions                                                                       spicy, powdery and                                        1-8 consisting of compounds                                                                       anise aroma                                               having the structures:                                                         ##STR78##                                                                    and                                                                            ##STR79##                                                                    Perfume composition prepared                                                                      A minty, spicy, herbal                                    according to Example II                                                                           and floral aroma                                                              increasing in intensity                                                       on dry-out                                                Product produced according to                                                                     Peppery, herbaceous,                                      Example III, bulked fractions                                                                     spearmint, caraway                                        3-8, consisting of the compounds                                                                  aroma with basil and                                      having the structures:                                                                            aniseed undertones                                         ##STR80##                                                                    and                                                                            ##STR81##                                                                    Perfume compositions prepared                                                                     A minty, spicy, herbal                                    according to Example IV                                                                           and floral aroma                                                              increasing in intensity                                                       on dry-out                                                ______________________________________                                    

EXAMPLE VII

The following shampoo is prepared containing the following ingredients:

    ______________________________________                                        Ingredients           Parts by Weight                                         ______________________________________                                        Tridecyloxy polyethoxy ethanol                                                of ten ethoxy groups  17.3                                                    Polyoxyethylene (20) sorbitan                                                 monolaurate           7.5                                                     Myristyl dimethylamine oxide                                                  (30% active)          25.0                                                    C.sub.10 -C.sub.20 fatty acyl monoethanolamide                                (cocomonoethanolamide)                                                                              2.5                                                     Polyacrylamide of molecular weight                                            of about 1,500,000    0.2                                                     Hydrogen peroxide (30% aqueous                                                solution)             0.5                                                     Perfume ingredient as indicated at                                            Table III (below) giving rise to                                              the aroma profiles as indicated in                                            Table III (below)     1.0                                                     Deionized water (3 micromhos/cm                                               conductivity          46.0                                                    ______________________________________                                    

A shampoo of the above composition is made in the following manner.First, the tridecyloxy polyethoxy ethanol is added to a clean mixingtank, with the agitator on, and the amine oxide, polyoxyethylenesorbitan monolaurate and cocomonoethanolamine are added sequentially,with continued agitation. The mix is then heated to 68° C., until thecocomonoethanolamide is melted and/or dissolved. The hydrogen peroxidesolution is then admixed with the mentioned nonionics and mixing iscontinued for about half an hour, in which the peroxide destroys anyfree amines or other harmful impurities that may be present. The mix isthen cooled to 38° C.

In a separate mixer the polyacrylamide is gradually added to the formulaweight of deionized water, with the mixer on. Addition is effectedcarefully and slowly (the polyacrylamide is sprinkled in) to avoid theproduction of "fish eyes" in the mix. After dissolving of thepolyacrylamide the solution thereof is added to the first mixing tankwith agitation and is blended with the nonionics, such mixings being atroom temperature. Subsequently, the perfume as indicated in Table III(below) giving rise to the aroma profile as set forth in Table III(below) is admixed with the balance of the composition and mixing iscontinued for another half hour.

                  TABLE III                                                       ______________________________________                                        Product             Aroma Profile                                             ______________________________________                                        Product produced according                                                                        Herbaceous, spearmint,                                    Example I, bulked fractions                                                                       spicy, powdery and                                        1-8 consisting of compounds                                                                       anise aroma                                               having the structures:                                                         ##STR82##                                                                    and                                                                            ##STR83##                                                                    Perfume composition prepared                                                                      A minty, spicy, herbal                                    according to Example II                                                                           and floral aroma                                                              increasing in intensity                                                       on dry-out                                                Product produced according to                                                                     Peppery, herbaceous,                                      Example III, bulked fractions                                                                     spearmint, caraway                                        3-8, consisting of the compounds                                                                  aroma with basil and                                      having the structures:                                                                            aniseed undertones                                         ##STR84##                                                                    and                                                                            ##STR85##                                                                    Perfume compositions prepared                                                                     A minty, spicy, herbal                                    according to Example IV                                                                           and floral aroma                                                              increasing in intensity                                                       on dry-out                                                ______________________________________                                    

The product made is an excellent shampoo of satisfactory viscosity andaroma, foaming power, foam stability, low conductivity and goodshampooing effects. The viscosity is about 1,000 centipoises at 20° C.and the conductivity, using the Hach Conductivity Meter, is 750micromhos/cm. The foaming power is 250 ml. and the foam stability is 22seconds, by the test method previously described. In comparison, acommercial shampoo based on triethanolamine lauryl sulphate detergenthas a conductivity of about 22,000 micromhos/cm, a viscosity of about1,500 centipoises, a foaming power of about 380 ml. and a foam stabilityof 60 seconds.

In panel evaluations of the experimental shampoo compared to a differentcommercial product, in actual shampooing, the experimental formula wasadjudged significantly better in being less drying, producing a softerfeel for the wet hair, leaving the wet hair easier to comb, being lessprone to accumulate static charges (less flyaway) and having a foam ofbetter appearance and feel. Additionally, the experimental product wasjudged better in almost all hair effect properties, with the controlonly being about equal to it in curl retention. In properties other thanthose mentioned, the experimental product was better in rinsability, thecontrol was better in foam build-up rate and the foams were about equalin volume and stability.

In the shampooing described herein and in subsequent Examples the humanhair is washed on the head by wetting the hair with warm tap water atabout 42° C., applying 15 grams of shampoo to the hair, lathering itinto the hair for a minute, rinsing with warm tap water for 30 seconds,re-lathering with 7 grams of shampoo for a minute and rinsing off for 30seconds, after which the hair is towel dried and dried further with anautomatic hair dryer.

EXAMPLE VIII Fabric Freshener Composition

A fabric fastener composition is prepared as follows:

    ______________________________________                                        Ingredients         Parts by Weight                                           ______________________________________                                        Sodium bicarbonate  3                                                         "Kyro" EOB (Trademark)*                                                                           1                                                         Perfume ingredient as set forth                                               in Table IV (below) giving rise                                               to an aroma as set forth in                                                   Table IV (below)    1                                                         Water               0.05                                                      ______________________________________                                    

The composition of this Example is prepared by simply mixing theingredients.

The above described composition is applied to a lightly soiled andwrinkled fabric as droplets (ca. 5.0 mm avg. size) using a triggeraction sprayer having a nozzle which is adjustable to providecomposition droplets in the desired range. The composition is applied ata rate of about 1 gram of composition to about 10 grams of fabric.

The fabric is then placed in an automatic dryer and dried, with tumblingaction, at a temperature of 60° C.-80° C. for a period of 15 minutes.The fabric is rendered free of wrinkles and static, and has a freshappearance and pleasant odor profile as set forth in Table IV below.

In the foregoing procedure, substantially the same results were obtainedwhen sodium carbonate is substituted for the sodium bicarbonate.

                  TABLE IV                                                        ______________________________________                                        Product             Aroma Profile                                             ______________________________________                                        Product produced according                                                                        Herbaceous, spearmint,                                    Example I, bulked fractions                                                                       spicy, powdery and                                        1-8 consisting of compounds                                                                       anise aroma                                               having the structures:                                                         ##STR86##                                                                    and                                                                            ##STR87##                                                                    Perfume composition prepared                                                                      A minty, spicy, herbal                                    according to Example II                                                                           and floral aroma                                                              increasing in intensity                                                       on dry-out                                                Product produced according to                                                                     Peppery, herbaceous,                                      Example III, bulked fractions                                                                     spearmint, caraway                                        3-8, consisting of the compounds                                                                  aroma with basil and                                      having the structures:                                                                            aniseed undertones                                         ##STR88##                                                                    and                                                                            ##STR89##                                                                    Perfume compositions prepared                                                                     A minty, spicy, herbal                                    according to Example IV                                                                           and floral aroma                                                              increasing in intensity                                                       on dry-out                                                ______________________________________                                    

EXAMPLE IX Perfumed Liquid Detergent

Concentrated liquid detergents (lysine salts of n-dodecyl benzenesulfonic acid as more specifically described in U.S. Pat. No. 3,948,818,issued on Apr. 6, 1976) with aromas as indicated in Table V below areprepared containing 0.10%, 0.15%, 0.20%, 0.25%, 0.30%, 0.40%, 0.50% and0.80% of the perfume ingredient as set forth in Table V below. Thedetergents are prepared by adding and homogeneously mixing theappropriate quantity of perfume ingredient as set forth in Table Vbelow. The detergents all possess aromas as set forth in Table V belowwith the intensity of each increasing with greater concentrations of theperfume ingredient as indicated in Table V below.

                  TABLE V                                                         ______________________________________                                        Product              Aroma Profile                                            ______________________________________                                        Product produced according                                                                         Herbaceous, spearmint,                                   Example I, bulked fractions                                                                        spicy, powdery and                                       1-8 consisting of compounds                                                                        anise aroma                                              having the structures:                                                         ##STR90##                                                                    and                                                                            ##STR91##                                                                    Perfume composition prepared                                                                       A minty, spicy, herbal                                   according to Example II                                                                            and floral aroma                                                              increasing in intensity                                                       on dry-out                                               Product produced according to                                                                      Peppery, herbaceous,                                     Example III, bulked fractions                                                                      spearmint, caraway                                       3-8, consisting of the compounds                                                                   aroma with basil and                                     having the structures:                                                                             aniseed undertones                                        ##STR92##                                                                    and                                                                            ##STR93##                                                                    Perfume compositions prepared                                                                      A minty, spicy, herbal                                   according to Example IV                                                                            and floral aroma                                                              increasing in intensity                                                       on dry-out                                               ______________________________________                                    

EXAMPLE X Preparation of a Cologne and Handkerchief Perfume

The perfume ingredient as set forth in Table VI below is incorporatedinto colognes at concentrations of 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 5.0%and 6.0% in 75%, 80%, 90% and 95% aqueous ethanol solutions. Distinctand definite aromas as set forth in Table VI below are imparted to thecolognes. The perfume ingredients as indicated in Table VI below arealso added to handkerchief perfumes at concentrations of 15%, 20%, 25%,30% and 35% (in 75%, 80%, 90% and 95% aqueous ethanol) and aromaprofiles as set forth in Table VI are imparted to the handkerchiefperfume.

                  TABLE VI                                                        ______________________________________                                        Product              Aroma Profile                                            ______________________________________                                        Product produced according                                                                         Herbaceous, spearmint,                                   Example I, bulked fractions                                                                        spicy, powdery and                                       1-8 consisting of compounds                                                                        anise aroma                                              having the structures:                                                         ##STR94##                                                                    and                                                                            ##STR95##                                                                    Perfume composition prepared                                                                       A minty, spicy, herbal                                   according to Example II                                                                            and floral aroma                                                              increasing in intensity                                                       on dry-out                                               Product produced according to                                                                      Peppery, herbaceous,                                     Example III, bulked fractions                                                                      spearmint, caraway                                       3-8, consisting of the compounds                                                                   aroma with basil and                                     having the structures:                                                                             aniseed undertones                                        ##STR96##                                                                    and                                                                            ##STR97##                                                                    Perfume compositions prepared                                                                      A minty, spicy, herbal                                   according to Example IV                                                                            and floral aroma                                                              increasing in intensity                                                       on dry-out                                               ______________________________________                                    

EXAMPLE XI Grapefruit Formulation

The following formulation is prepared:

    ______________________________________                                        Ingredients            Parts by Weight                                        ______________________________________                                        Grapefruit oil         88                                                     Nootkatone             4                                                      Bergamot oil;          2                                                      Citral                 3                                                      Amyl alcohol           1                                                      Ethyl acetate          1                                                      5-Phenyl-4-pentenal    1                                                      N,N-1, (and 5)-Trimethyl-5-norbornane                                         2-carboxamide, prepared according to                                          Ex. III (bulked fractions 3-8)                                                                       0.5                                                    ______________________________________                                    

When the above grapefruit formulation is added to water at the rate of1%, an excellent grapefruit drink is prepared. The N,N-1(and5)-Trimethyl-5-norbornane 2-carboxamide prepared according to Example II(bulked fractions 3-8) gives an intense sweet, anise note to the instantformulation, thereby rendering it more desirable. Additional quantitiesof the N,N-1 (and 5)-Trimethy-5-norbornane 2-carboxamides preparedaccording to Example III, (e.g., one additional part by weight) canreplace the nootkatone in the grapefruit formulation.

The foregoing grapefruit formulation can also be enhanced by one or moreof the following materials at one part by weight:

4-Mercapto-5-nonanone (prepared according to U.S. Pat. No. 4,064,278)

4-Mercapto-5-nonanol (prepared according to U.S. Pat. No. 4,064,278)

3-Mercapto-2,6-dimethyl-4-heptanone (prepared according to U.S. Pat. No.4,064,278)

2-Mercapto-3-pentanone (prepared according to U.S. Pat. No. 4,064,278)

3-Mercapto-4-heptanol (prepared according to U.S. Pat. No. 4,064,278)

Thus, our invention is also intended to cover the mixtures of alpha-oxy(oxo) Mercaptans and N,N-1 (and 5)-Trimethyl-5-norbornane 2-carboxamidesand the corresponding unsaturated norbornane derivative(s) in ratios of0.01 parts by weight alpha-oxy (oxo) Mercaptan: 1 part by weightnorbornane derivative(s) up to 0.01 parts by weight norbornanederivative(s): 1 part by weight alpha-oxy (oxo) Mercaptan of U.S. Pat.No. 4,064,278.

EXAMPLE XII A. Powder Flavor Composition

20 grams of the flavor composition of Example XI containing thecompounds having the structures: ##STR98## prepared according to ExampleII (bulked fractions 3 and 8) is emulsified in a solution containing 300grams gum acacia and 700 grams water. The emulsion is spray-dried with aBowen Lab Model Drier utilizing 260 c.f.m. of air with an inlettemperature of 500° F., an outlet temperature of 200° F., and a wheelspread of 50,000 rpm.

B. Sustained Release Flavor

The following mixture is prepared:

    ______________________________________                                        Ingredients           Parts by Weight                                         ______________________________________                                        Liquid Grapefruit Flavor                                                                            20                                                      of Example XI                                                                 Propylene Glycol      9                                                       Cab-O-Sil® M-5                                                            (Brand of Silica produced by the                                              Cabot Corporation of 125 High Street                                          Boston, Mass. 02112                                                           Physical Properties:                                                          Surface area: 200 m.sup.2 /gm                                                 Nominal particle size: 0.012 microns                                          Density: 2.3 lbs/cu. ft.)                                                                           5.00                                                    ______________________________________                                    

The Cab-O-sil is dispersed in the liquid grapefruit flavor compositionof Example XI with vigorous stirring, thereby resulting in a viscousliquid. 71 parts by weight of the powder flavor composition of Part A,supra, is then blended into the said viscous liquid, with stirring at25%C. for a period of thirty minutes, thereby resulting in a dry,free-flowing sustained release grapefruit flavor powder.

EXAMPLE XIII

10 parts by weight of 5 -Bloom pigskin gelatin is added to 90 parts byweight of water at a temperature of 150° F. The mixture is agitiateduntil the gelatin is completely dissolved and the solution is cooled to120° F. 20 parts by weight of the liquid grapefruit flavor compositionof Example XI is added to the solution which is then homogenized to forman emulsion having particle size typically in the range of 2-5 microns.This material is kept at 120° F. under which conditions the gelatin willnot gel.

Coacervation is induced by adding, slowly and uniformly, 40 parts byweight of a 20% aqueous solution of sodium sulphate. Duringcoacervation, the gelatin molecules are deposited uniformly about eachoil droplet as a nucleus.

Gelatin is effected by pouring the heated coacervate mixture into 1,000parts by weight of 7% aqueous solution of sodium sulphate at 65° F. Theresulting gelled coacervate may be filtered and washed with water attemperatures below the melting point of gelatin, to remove the salt.

EXAMPLE XIV Chewing Gum

100 Parts by weight of chicle are mixed with 4 parts by weight of theflavor prepared in accordance with Example XII. 300 Parts of sucrose and100 parts of corn syrup are added. Mixing is effected in a ribbonblender with jacketed side walls of the type manufactured by the BakerPerkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inchin width and 0.1 inches in thickness. The strips are cut into lengths of3 inches each. On chewing, the chewing gum has a pleasant, long lastinggrapefruit flavor.

EXAMPLE XV Chewing Gum

100 parts by weight of chicle are mixed with 18 parts by weight of theflavor prepared in accordance with Example XIII. 300 parts of sucroseand 100 parts of corn syrup are added. Mixing is effected in a ribbonblender with jacketed walls of the type manufactured by the BakerPerkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inchin width and 0.1 inches in thickness. The strips are cut into lengths of3 inches each. On chewing, the chewing gum has a pleasant, long lastinggrapefruit flavor.

EXAMPLE XVI Toothpaste Formulation

The following separate groups of ingredients are prepared:

    ______________________________________                                        Parts by Weight  Ingredient                                                   ______________________________________                                        Group "A"                                                                     30.200           Glycerine                                                    15.325           Distilled Water                                               .100            Sodium Benzoate                                               .125            Saccharin Sodium                                              .400            Stannous Fluoride                                            Group "B"                                                                     12.500           Calcium Carbonate                                            37.200           Dicalcium Phosphate                                                           (Dihydrate)                                                  Group "C"                                                                     2.000            Sodium n-Lauroyl                                                              Sarcosinate (foaming                                                          agent)                                                       Group "D"                                                                     1.200            Flavor Material of                                                            Example XII                                                  100.00 (Total)                                                                ______________________________________                                    

Procedure:

1. The ingredients in Group "A" are stirred and heated in a steamjacketed kettle to 160° F.

2. Stirring is continued for an additional three to five minutes to forma homogeneous gel.

3. The powders of Group "B" are added to the gel, while mixing, until ahomogeneous paste is formed.

4. With stirring, the flavor of "D" is added and lastly the sodiumn-lauroyl sarcosinate.

5. The resultant slurry is then blended for one hour. The completedpaste is then transferred to a three roller mill and then homogenized,and finally tubed.

The resulting toothpaste, when used in a normal toothbrushing procedureyields a pleasant grapefruit flavor, of constant strong intensitythroughout said procedure (1-1.5 minutes).

EXAMPLE XVII Chewable Vitamin Tablets

The flavor material produced according to the process of Example XII isadded to a Chewable Vitamin Tablet Formulation at the rate of 10grams/kilogram which chewable vitamin tablet formulation is prepared asfollows:

In a Hobart Mixer the following materials are blended to homogeneity:

    ______________________________________                                                             Gms/1000 tablets                                         ______________________________________                                        Vitamin C (ascorbic acid) as ascorbic                                         acid-sodium ascorbate mixture 1:1                                                                    70.00                                                  Vitamin B.sub.1 (thiamine mononitrate) as                                     Rocoat® thiamine mononitrate 331/3%                                       (Hoffman La Roche)     4.0                                                    Vitamin B.sub.2 (riboflavin) as Rocoat®                                   riboflavin 331/3%      5.0                                                    Vitamin B (pyridoxine hydrochloride)                                          as Rocoat® pyridoxine hydrochloride                                       331/3%                 4.0                                                    Niacinamide as Rocoat® niacinamide 331/3%                                                        33.0                                                   Calcium pantothenate   11.5                                                   Vitamin B.sub.12 (cyanocobalamin) as Merck 0.1%                               in gelatin             3.5                                                    Vitamin E (dl-alpha tocopheryl acetate)                                       as dry vitamin E acetate 331/3% Roche                                         d-biotin               6.6                                                    Flavor of Example XII  0.004                                                                         (as indicated above)                                   Certified lake color   5.0                                                    Sweetener - sodium saccharin                                                                         1.0                                                    Magnesium stearate lubricant                                                                         10.0                                                   Mannitol q.s. to make  500.00                                                 ______________________________________                                    

Preliminary tablets are prepared by sluggish with flat-faced punches andgrinding the slugs to 14 mesh. 13.5 g Dry Vitamin A acetate and 0.6 gVitamin D are then added as beadlets. The entire blend is thencompressed using concave punches at 0.5 g each.

Chewing of the resultant tablets yields a pleasant, long-lasting,consistently strong grapefruit flavor for a period of 12 minutes.

EXAMPLE XVIII Chewing Tobacco

Onto 100 pounds of tobacco for chewing (85% Wisconsin leaf and 15%Pennsylvania leaf) the following the following casing is sprayed at arate of 30%:

    ______________________________________                                        Ingredients         Parts by Weight                                           ______________________________________                                        Corn Syrup          60                                                        Licorice            10                                                        Glycerine           20                                                        Fig Juice           4.6                                                       Prune Juice         5                                                         Flavor Material of Example XII                                                                    0.4                                                       ______________________________________                                    

The resultant product is redried to a moisture content of 20%. Onchewing, this tobacco has an excellent substantially consistent, longlasting, licorice/grapefruit flavor profile in conjunction with thetobacco note.

EXAMPLE XIX Preparation ofN,N,5-Trimethyl-5-Norbornene-Endo-2-Carboxamide

Reaction: ##STR99##

Into a 1000 cc autoclave equipped for pressure reactions, is placed 104grams of methylcyclopentadiene dimer and 250 grams of N,N-dimethylacrylamide. The autoclave is closed and placed in a Parr shaker. Thecontents of the autoclave are heated to 200° C. while maintaining thepressure at 125-145 psig and with shaking maintained at that temperatureand pressure for a period of 7 hours.

At the end of the 7 hour period, the contents of the autoclave arecooled and the autoclave is opened. The reaction mass is then removedfrom the autoclave and distilled using a micro distillation apparatusyielding the following fractions:

    ______________________________________                                                  Vapor    Liquid   Head   Weight                                     Fraction  Temp.    Temp.    Vac.   of                                         Number    °C.                                                                             °C.                                                                             mm. Hg.                                                                              Fraction                                   ______________________________________                                        1         70/73    100/100  .6/.6  13.6                                       2         76       101      .6     12.3                                       3         78       114      .6     17                                         4         86       121      .6     17.9                                       5         91       124      .6     13                                         6         104      141      .8     18.1                                       7         99       142      .6     10.8                                       8         99       149      .6     14.7                                       9         99       184      .6     10.2                                       10        104      216      .6     6.2                                        ______________________________________                                    

The GLC profile prior to distillation is set forth in FIG. 8. The GLCconditions are: Carbowax column programmed at 80°-220° C. at 8° C. perminute. NMR and IR analysis confirm that the product produced has thestructure: ##STR100##

FIG. 9 is the NMR spectrum for the compound having the structure:##STR101##

FIG. 10 is the infra-red spectrum for the compound having the structure:##STR102##

The resulting compound has an excellent fruity aroma with acastoreum-like undertone. The material tested for its organolepticproperties results from the bulking of fractions 3-8 of the foregoingdistillation.

EXAMPLE XX Tobacco Formulation

A tobacco mixture is produced by admixing the following ingredients:

    ______________________________________                                        Ingredient      Parts by Weight                                               ______________________________________                                        Bright          40.1                                                          Burley          24.9                                                          Maryland        1.1                                                           Turkish         11.6                                                          Stem (flue-cured)                                                                             14.2                                                          Glycerine       2.8                                                           Water           5.3                                                           ______________________________________                                    

Cigarettes are prepared from this tobacco. The following flavorformulation is prepared:

    ______________________________________                                        Ingredient     Parts by Weight                                                ______________________________________                                        Ethyl butyrate .05                                                            Ethyl valerate .05                                                            Maltol         2.00                                                           Cocoa extract  26.00                                                          Coffee extract 10.00                                                          Ethyl alcohol  20.00                                                          Water          41.90                                                          ______________________________________                                    

The above stated tobacco flavor formulation is applied at the rate of0.1% to all of the cigarettes produced using the above tobaccoformulation. Half of the cigarettes are then treated with 500 to 1,500ppm of the N,N-1(and 5)-trimethyl-5-norbornene-2-carboxamide mixtureproduced according to Example I.

The control cigarettes not containing the norbornyl derivative and theexperimental cigarettes which contain the norbornyl derivative areevaluated by paired comparison and the results are as follows:

The experimental cigarettes are found, on smoking, to have a sweeter,fruity, more natural tobacco-like aroma prior to smoking and on smokingin the main stream and the side stream. The experimental cigarettescontaining the product produced according to Example I are basicallymore burley tobacco-like.

All cigarettes are evaluated for smoke flavor with a 20 mm celluloseacetate filter.

EXAMPLE XXI

The following minty, floral and herbal type formula is prepared:

    ______________________________________                                        Ingredient         Parts by Weight                                            ______________________________________                                        Geranium Bourbon   20.0                                                       Rosemary Oil Spanish                                                                             10.0                                                       Lavender Oil Barreme                                                                             10.0                                                       Thyme Oil White    10.0                                                       Amyl Cinnamic Aldehyde                                                                           10.0                                                       Sauge Sclaree French                                                                             5.0                                                        Sandalwood Oil     5.0                                                        Galbanum Oil       5.0                                                        Patchouli Oil Light                                                                              5.0                                                        Cedarwood Oil Light                                                                              15.0                                                       Product produced according to                                                                    45.0                                                       Example XIX, bulked fractions                                                 3-8 containing and consisting                                                 of the compound having the                                                    structure:                                                                     ##STR103##                                                                   ______________________________________                                    

When the composition of matter prepared according to Example XIX isincorporated into the formula at 45.0%, the composition of matter hasadded to it a pleasant fruity, castoreum-like, herbaceous, spearmint,spicy, powdery, floral, basis, caraway and anise aroma to the alreadyspicy, herbal and floral type formulation.

EXAMPLE XXII Preparation of a Cologne and Handkerchief Perfume

The perfurme ingredient as set forth in Table VII below is incorporatedinto colognes at concentrations of 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 5.0%and 6.0% in 75%, 80%, 90% and 95% aqueous ethanol solutions. Distinctand definitive aromas as set forth in Table VII below are imparted tothe colognes. The perfume ingredients as indicated in Table VII beloware also added to handkerchief perfumes at concentrations of 15%, 20%,25%, 30% and 35% (in 75%, 80%, 90% and 95% aqueous ethanol) and aromaprofiles as set forth in Table VII below are imparted to thehandkerchief perfume:

                  TABLE VII                                                       ______________________________________                                        Product             Aroma Profile                                             ______________________________________                                        Product produced according                                                                        A fruity, castoreum-like,                                 to Example XIX, bulked                                                                            herbaceous, spearmint,                                    fractions 3-8 consisting of                                                                       spicy, powdery and anise                                  the compound having the                                                                           aroma.                                                    structure:                                                                     ##STR104##                                                                   Perfume composition prepared                                                                      A minty, spicy, herbal                                    according to Example XXII                                                                         and floral aroma with                                                         important fruity and                                                          castoreum-like nuances                                                        increasing in intensity                                                       on dry-out.                                               ______________________________________                                    

EXAMPLE XXIII Perfumed Liquid Detergent

Concentrated liquid detergents (lysine salt of n-dodecyl benzenesulfonic acid as more specifically described in U.S. Pat. No. 3,948,818,issued on Apr. 6, 1976) with aromas as indicated in Table VIII below areprepared containing 0.10%, 0.15%, 0.20%, 0.25%, 0.30%, 0.40%, 0.50% and0.80% of the perfume ingredient as set forth in Table VIII below. Thedetergents are prepared by adding and homogeneously mixing theappropriate quantity of perfume ingredient as set forth in Table VIIIbelow. The detergents all possess aromas as set forth in Table VIIIbelow with the intensity of each increasing with greater concentrationsof the perfume ingredient as indicated in Table VIII below.

                  TABLE VIII                                                      ______________________________________                                        Product             Aroma Profile                                             ______________________________________                                        Product produced according                                                                        A fruity, castoreum-like,                                 to Example XIX, bulked                                                                            herbaceous, spearmint,                                    fractions 3-8 consisting of                                                                       spicy, powdery and anise                                  the compound having the                                                                           aroma.                                                    structure:                                                                     ##STR105##                                                                   Perfume composition prepared                                                                      A minty, spicy, herbal                                    according to Example XXII                                                                         and floral aroma with                                                         important fruity and                                                          castoreum-like nuances                                                        increasing in intensity                                                       on dry-out.                                               ______________________________________                                    

What is claimed is:
 1. A product containing a major proportion ofisomers defined according to the structures: ##STR106## producedaccording to the process of reacting methyl cyclopentadiene having thestructure: ##STR107## with N,N-dimethyl acrylamide in the presence of acatalyst defined according to the formula:

    R'.sub.n AlCl.sub.m

wherein R' is C₁ -C₃ alkyl and the sum, m+n=3 with m being 1 or 2 and nbeing 1 or 2 at a temperature in the range of from about 0° C. up toabout 50° C.
 2. A product containing a major proportion of compoundsdefined according to the structures: ##STR108## produced according tothe process of: (a) Reacting N,N-dimethyl acrylamide with methylcyclopentadiene having the structure: ##STR109## in the presence of acatalyst defined according to the formula:

    R'.sub.n AlCl.sub.m

wherein R' is C₁ -C₃ alkyl and the sum, m+n=3 with m being 1 or 2 and nbeing 1 or 2 at a temperature in the range of from about 0° C. up toabout 50° C. whereby a mixture of isomers containing a major proportionof compounds defined according to the structures: ##STR110## are formedand then (b) Hydrogenating the resulting reaction product at pressuresof from about 20 psig up to about 2,000 psig in the presence of acatalyst selected from the group consisting of Raney Nickel, palladiumon carbon, palladium on calcium carbonate, palladium on barium sulfateand platinum.